Shampoo composition



United States Patent Office 33,3l3J35 Patented Apr. 11, 1567 3,313,735 HAMPGO CGMPOSITION Homer W. McCune, Wyoming, Ohio, assignor to The Procter & Gamble Company, Cincinnati, Ohio, a cor- -oration of Bhio i Drawing. Fiied Sept. 25, 1963, Ser. No. 311,633

12 Claims. (Cl. 252-452) This invention relates to a shampoo composition which improves the manageability of the washed hair. More particularly this invention relates to a shampoo composition characterized by its content of certain alkylphosphonic acids and salts thereof which provide an adherent lubricating lm to the hair surfaces, rendermg the hair more manageable. I

The active ingredients of shampoo compositions which are currently commercially available generally consist of a major proportion of soap, or of non-soap synthetic anionic or nonionic detergents in an aqueous medium (liquid to cream paste) to which are added one or more various auxiliary ingredients such as opacifiers, clanfying agents, suds boosters, antidandruif agents, etc. in minor proportions. When the hair is washed with a shampoo containing such non-soap synthetic detergents as the cleansing agent, much of the natural oil of the hair is removed, making the washed hair diificult to manage unless measures are taken to overcome this effect. Hair manageability (the relative ease with which the hair can be placed in a desired coiifure) is influenced by hair lubricity and entanglement, i.e., combability (pronounced comb-ability), and by electrostatic charge causing hair KSfly-77 The adverse effect of shampoos containing synthetic detergents on hair manageability has been recognized by those skilled in the art and attempts have been made to overcome this effect. For example, finishing agents such as lanolin and its derivatives, mineral oil, and polyglycol stearate have been added to shampoos so that the hair is left in a conditioned state after washing. However, the incorporation of these additional agents into the shampoo impairs lathering or leaves a sticky film on the hair.

It is an object of this invention to provide a shampoo which improves the manageability of the hair yet which possesses good lathering and cleaning characteristics.

ther objects and benefits of this invention will be apparent from the following description thereof.

In general, the shampoo compositions of this invention are comprised of from about 10% to about 30% by weight of a non-soap anionic organic synthetic detergent, from about 0.2% to about 5% by weight of certain alkyl phosphonic acids or water-soluble salts thereof (hereinafter referred to as phosphono compounds) and the balance substantially water, the .pH of the composition being in the range of from about 6.0 to about 10.0.

The phosphono compounds which find utility in the compositions of this invention are those having the general formulae:

( P OaMz R J-X where R is an alkyl radical containing from about 6 to about 18 carbon atoms, X is selected from the group consisting of hydrogen and methyl, Z is selected from the group consisting of OH, COOM, and PO M radicals, and M is selected from the group consisting of hydrogen, sodium, potassium, ammonium, and low molecular Weight substituted ammonium.

Representative operable compounds include the alkylaminodi(methylphosphonic acids), and the alkali metal, ammonium, and substituted ammonium salts thereof, including hexylarninodi(methylphosphonic acid), octylaminodi(methylphosphonic acid), dodecylaminodi(methylphosphonic acid), sodium tetradecylaminodi(methylphosphonate), and monoethanolammonium octadecylaminodi(methylphosphonate); the alkylphosphonoacetic acids and the alkali metal, ammonium and substituted ammonium salts thereof, including hexylphosphonoacetic acid, sodium nonylphosphonoacetate, potassium tetradecylphosphonoacetate, potassium hexadecylphosphonoacetate, and monoethanolammonium octadecylphosphonoacetate; the l-hydroxy-l-methylalkylphosphonic acids and the alkali metal, ammonium, and substituted ammonium salts thereof, including l-hydroxy-l-methyldecylphosphonic acid, sodium l-hydroxy-1-methyltetradecylphosphonate, ammonium l-hydroXy-l-methylhexadecylphosphonate, diethanolammonium l-hydroxy-l-methyloctadecylphosphonate; the l-hydroxyalkylphosphonic acids and the alkali metal, ammonium, and substituted ammonium salts thereof, including l-hydroxyhexylphosphonic acid, sodium 1-hydroxydodecylphosphonate, and ammonium l-hydroxyhexadecylphosphonate; l-methyldecylphonoacetic acid, sodium l-methyldodecylphosphonoacetic acid; the alkylidenediphosphonic acids and the alkali metal, ammonium, and substituted ammonium salts thereof, including decylidenediphosphonic acid, sodium tridecylidenediphosphonate, ammonium pentadecylidenediphosphonate, ammonium hexadecylidenediphos- .phonate, and monoethanolammonium octadecylidenediphosphonate; tetradecane-Z,Z-diphosphonic acid, and sodium tetradecane 2,2-diphosphonate.

Preferred phosphono compounds for use in the shampoo compositions of this invention include the sodium, potassium, and low molecular weight substituted ammonium salts of alkylaminodi(methylphosphonic acid) where the alkyl radical is nonyl, decyl, undecyl, dodecyl, tridecyl, and tetradecyl. These compounds are preferred because they are exceptionally efficacious in improving hair manageability, by enhancing combability and reducing the electrostatic charge which causes hair fly in the Washed hair. Other compounds which are particularly suitable include dodecylphosphonoacetic acid and the water-soluble salts thereof, dodecylidenediphosphonic acid, tridecylidenediphosphonic acid, l-hydroxy-l-methyldodecylphosphonic acid, l-hydroxy-l-methylhexadecylphosphonic acid and l-hydroxydodecyl phosphonic acid and water-soluble salts thereof.

The acid forms of the phosphoric compounds described above are less soluble in water than the salt forms and consequently are more difiieult to dissolve in the solvent system of a shampoo; thus in stating that the acid forms can be used in the shampoo compositions of this invenvention it is meant that they can be used subject to adjustment to the pH range more fully specified later herein.

The phosphono compounds to be used herein can be prepared by methods well known in the art. For example, the alkylamino(diphosphonic acids) can be prepared by reacting a primary amine with chloromethylphosphonic acid in alkaline solution according to the following equation:

This procedure is fully described by Schwartzenbach et al., Helv. Chim. Acta, 32, 1175 (1949).

The alkylphosphonoacetic acids can be prepared by alkylation at the central carbon atom of trialkyl phosphonoacetates, i.e., compounds of the general type (RO) P (O) CH CO R 9 .9 This method is fully described by G. M. Kosolopoff and J. S. Powell, J. Amer. Chem. Soc., 72, 4198 (1950).

The l-hydroxy-l-methylalkylphosphonic acids and l-hydroxyalkylphosphonic acids can be prepared by reacting an appropriate ketone with monoor dihalophosphines in accordance with the methods fully described by Stevens et al., U.S. Patent 2,254,124, granted Aug. 26, 1941.

Alkylidinediphosphonic acids can be prepared by salkylation. at the central carbon atom of tetralkyl methane diphosphonates with an alkyl halide in accordance with the method described by G. M. Kosolopoff in J. Amer. Chem. Soc., 75, 1500 (1953).

While this invention is not intended to be limited by the suggested mechanism whereby improved manageability is achieved, it is postulated that the phosphono compounds employed in the shampoo of this invention when used in water which contains natural hardness, i.e., Ca++ and Mg++ ions (as is almost always the case), react with these ions to form a precipitate on the hair during the shampooing operation. This precipitate adheres to the hair and renders the hair fibers lubricous and reduces entanglement, permitting ready placement of the hair in a desired coiffure while still wet. After the washed hair has dried, the retained precipitate reduces the electrostatic charge built up on the hair fiber by combing or brushing, essentially eliminating hair fly. This latter effect will in many cases be noted even through the sham poo is used with demineralized water so that it is postulated that some effect is produced by adsorption of the phosphono compound itself.

Thus this invention also encompasses the process of conditioning and increasing the combability of hair by shampooing the hair in the presence of calcium and magnesium ions in solution with the compositions of this invention. The hair can be shampooed in the conventional manner which comprises applying the shampoo composition to the hair and thoroughly admixing water containing calcium and magnesium ions therewith to work up a lather, working the lather into the hair, and then finally rinsing the hair with water, whereby the phosphono compounds are left precipitated on the hair to condition and improve the manageability of it.

It is desirable to use the phosphono compounds at concentrations ranging from about 0.2% to about 5.0% by weight of the total shampoo composition. Levels of about 0.2% and above are desired so that a significant improvement in hair manageability is observed. Concentrations above about 5.0% cause formulation problems, and the effect on hair manageability is not noticeably increased at levels higher than about 5.0%. Moreover, at higher concentrations too much deposition can occur and the hair feels dirty and. lacks luster.

Operable non-soap anionic organic detergents which are employed in the compositions of this invention include, for example, water-soluble salts of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 18 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. Important examples of the detergents of this group are the sodium or potassium alkyl sulfates, especially those derived by sulfation of higher alcohols produced by reduction of glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, especially those of the types described by Guenther et al. in U.S. Patent 2,220,099, granted November 5, 1940, and by Lewis in U.S. Patent 2,477,383, granted July 26, 1949, in which the alkyl group contains from about 9 to about carbon atoms; sodium alkylglycerylether sulfonates, especially those others in which the alkyl group is derived from the higher alcohols obtained from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates, sodium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about three moles of ethylene oxide, and. Others known in the art, a number being specifically set forth in Byerly, U.S. Letters Patent 2,485,921, granted November 1, 1949, and Strain, U.S. Letters Patent 2,486,922, granted November 1, 1949.

Additional non-soap anionic organic synthetic detergents which can be used in this invention include the salts of condensation products of fatty acids with sarcosine, i.e., acyl sarcosinates, wherein the acyl radical has a chain length ranging from about 10 to about 18 carbon atoms.

Preferred detergents are triethanolarnine and sodium salts of alkyl sulfate where the alkyl group averages about 12 carbon atoms, sodium and triethanolammonium alkylglycerylether sulfonate where the alkyl group averages about 12 carbon atoms, and the sodium and triethanolamine salts of the condensation product of 1 mole of coconut fatty alcohol and 3 moles of ethylene oxide.

The detergent can be employed in varying concentrations in the compositions of this invention ranging from about 10 to about 30% by weight; but preferably constitutes from about 15% to about 25% by Weight of the composition.

It is essential that the pH of the compositions of this invention be greater than about 6.0 and less than about 10.0. At pHs below about 6.0 the phosphono compounds of this invention are present in their less soluble (acid) forms and thereby reduce the sudsing ability of the shampoo. At a pH above about 6.0 the phosphono compounds are more soluble and do not materially impair the sudsing ability of the shampoo. At a pH above about 10.0 the shampoo compositions of this invention tend to irritate the eyes and skin. The preferred pH range is from about 7 to about 8.

The addition of the phosphono compounds in their acid forms to the other ingredients of the shampoo compositions of this invention results in a shampoo having a pH below about 6.0; thus the pH must be adjusted to the essential range, i.e., a base must be added. Suitable bases include, for example, triethanolamine, diethanolamine, monoethanolamine, sodium hydroxide, and potassium hydroxide.

Various minor ingredients though not essential, can be added to make the product more attractive in appearance or use. Among these are: sufficient dye to impart an attractive color to the shampoo; up to 1% or more of a sequestering agent to clarify solutions made from hard water; and up to 1% or more perfume. Up to about 5% of coconut diethanolamide and coconut monoethanolamide, the acyl radicals being derived from the middle cut of coconut fatty acid and containing predominantly 12 carbon atoms, can be added for their desirable effect on the feel of the hair and to enhance the sudsing ability. Organic solvents, for example, ethyl alcohol, can be added to the shampoo to increase solubility of the surfactants in the solvent system (water) or control viscosity. The water content can vary depending upon whether a paste or a liquid is desired.

To formulate a product having a paste consistency, the water content is generally maintained in the range from about to about by weight. Liquid shampoos generally contain more than about by weight water to insure a homogeneous solution over a satisfactory range of temperatures. Preferably the water content in all cases should be more than about 45 but less than about to insure sufiicient active material per unit volume.

This invention is more readily understood from the following examples.

Example I In this example the lather volume achieved by various representative shampoo compositions of this invention is compared with the lather volume achieved by a control composition identical in formulation but without the essential phosphono compound, to show that this conditioning agent does not materially afiect the lathering capacity of the shampoo. The lather volume of the shampoo compositions listed in Table 1 below was measured by homogeneously admixiiig 5.0 gms. of shampoo composition with the amount of synthesized sebum soil (a standardized soil containing in admixture, by weight, 33 /s% triglyceride fats, 33 /a% fatty acids, and 33 /3% cholesterol, lanolin, and unsaturated oils) indicated in Table 1 below, placing the mixture in a Waring Blendor with a specially adapted container on which is fused a 500 ml. volumetric cylinder, and adding water at 90 F. (about 250-300 cc.) to bring the volume up to the 0 line of the graduated cylinder. The solution was then agitated for seconds at 12,000 rpm. and the volume of the lather produced in the graduated cylinder was measured. The formula of the control product used in this test was as follows:

triethanolammonium coconut sulfate, the alkyl radical being derived from the middle cut of coconut alcohol and containing predominantly 12 carbon atoms; 5% coconut diethanolamide, the acyl radical being derived from the middle cut of coconut fatty acid and containing predominantly 12 carbon atoms; 7% ethanol, 0.25% perfume, and 67.75% Water. The pH of the product was adjusted to 7.4 with sodium hydroxide.

available shampoo composition (Shampoo Composition A) more fully described below containing no hair conditioning additives and the combing friction of each individual switch was measured by pulling the switch through a standard comb (Dura Flex #43, Colanite-(ee Products Company, Seaford, N.Y.) attached to a force transducer.

The comb is attached to a force transducer generating an electrical signal of which the voltage varies with the force required to pull the comb through the hair switch. This signal is suitably amplified, integrated, and recorded. The total work done on each pass of the comb through the switch is thus determined in foot pounds.

After the three test switches were shampooed with the control composition (Shampoo Composition A) and the total frictional force (work) exerted on the comb by a given length of each switch measured, one of the switches was shampooed with Shampoo Composition B, one with Shampoo C, and one with Shampoo Composition D, and the total frictional force exerted on the comb by the same length of each switch was again measured according to the method described above.

In the following table, Shampoo Composition A, the control shampoo, was a commercially available anionic detergent based liquid shampoo composition containing TABLE I Water Hardness 1 2 s-p-e- 12 5-1 8 2 g 1 -3 12 g.p.g. 2 g.p.g. 12 g.p.g.

Shampoo Composition Soil Load 0 0 I 0.5 gm. 0.5 gm. 1.0 gm. 1.0 gm.

1. Control (ml) 240 250 160 160 so 2. Control plus 0.5% by wt. Compound A 2 ml, 225 270 90 85 3. Control plus 1.0% by wt. Compound A 2 l Hardness is the total concentration of Ca++ and Mg++ ions expressed in terms of the equivalent amount of a 0 in grams per gallon (g.p.g. 1 Compound A tetradecylarninodi(methylphosphonic acid).

The pH of compositions (2) and (3) was readjusted to 7.4 with NaOH after addition of Compound A.

It can be seen from the above example that the lather- 5 20.0%

mg capacity of a shampoo containing tetradecylaminodi(methylphosphonic acid) a representative phosphono compound used in the compositions of this invention, is approximately the same as the control shampoo under various conditions of water hardness and soil load.

Example II The improved manageability of hair shampooed with the compositions of this invention can be demonstrated by measuring the combing friction of hair switches shampooed with the compositions of this invention and comparing the values obtained with the combining friction of the same hair switches Washed in conventional shampoo compositions. Reduction in the friction indicates greater hair lubricity and reduced entanglement, i.e., improved combability.

In this example, three uniform 12 gram switches of towel dried wet hair about 13 to 15 inches in length were shampooed with a good conventional commercially by weight triethanolammonium alkyl sulfate (the alkyl group obtained from coconut alcohol and containing predominantly 12 carbon atoms), and also containing inor proportions of perfume, color, clarifying agents, and alcohol to adjust the viscosity, the balance substantially water. The pH of the shampoo was adjusted to 7.3 with NaOH.

Shampoo Composition B had the same composition as A, with the exception that 1% by weight of tetradecylaminodi(methylphosphonic acid) was added thereto. The pH was adjusted to 7.3 with NaOH.

Shampoo Composition C had the same composition as A with the exception that 1% .by weight of dodecylphosphonoacetic acid was added thereto. The pH was adjusted to 7.3 with NaOH.

Shampoo Composition D had the same composition as A with the exception that 1% by weight of l-hydroxy- 1-methyl-hexadecylphosphonic acid was added thereto. The pH was adjusted to 7.3 with NaOH.

TABLE II Switch #1 Switch #2 Switch #3 1st Pass 2d Pass 1st Pass 2d Pass 1st Pass 2d Pass Ft. lbs. Ft. lbs. Ft. lbs Shampoo Composition A (Control) 222 1. 11 5 Shampoo Composition B Shampoo Composition C .127 Shampoo Composition D i .236 .206

It is seen from the above table that the combing friction of hair switches shampooed with the representative compositions of this invention (Shampoos B, C, and D) above is markedly less than switches washed with a typical commercially available shampoo (Shampoo A) reflecting the greater hair lubricity and reduced entanglement of the switches shampooed with the compositions of this invention. Hair which is in this condition after washing can be easily arranged in a desired coitfure while still wet.

Example III A shampoo is prepared having the following composition:

Percent by weight Sodium alkyl sulfate 24.0 Methyl cellulose 1.3 Ammonium sulfite .30 Tetrasodium ethylenediaminetetraacetate .20 Tetradecylaminodi(methylphosphonic acid) 2.0 Perfume 3 Water and misc., plus Na-OH to adjust to pH 7 .4, balance.

1 Alkyl group derived from the middle cut of coconut fatty alcohol containing predominantly 12 carbon atoms.

This shampoo possesses excellent lathering and cleaning characteristics. It is markedly superior to conventional shampoos in reducing static electrification of dry hair on combing or brushing and consequently greatly reduces hair fly of hair which has been shampooed therewith in the conventional manner. Hair washed with this shampoo also exhibit improved combability.

Octadecylaminodi(methylphosphonic acid), dodecylaminodi (methylphosphonic acid) decylarninodi(methylphosphonic acid), or octylaminodi(methylphosphonic acid) or the sodium, potassium, ammonium and substituted ammonium salts thereof can be substituted for the tetradecylaminodi(methylphosphonic acid) in this formulation without substantially affecting the properties or performance of the shampoo.

Example IV Another shampoo is prepared having the formula indicated below:

Percent by weight Sodium alkylglycerylether sulfonate 25.0 Coconut 1 diethanolamide 4.0 Methyl cellulose 1.0 Tetrasodiurn ethylenediaminetetraacetate .10 Dodecylphosphonoacetic acid 1.0 Perfume 1.0

Water and misc., plus NaOH to adjust to pH 7.3, balance.

The alkyl or acyl group being derived from the middle cut of coconut fatty alcohol or fatty acid and containing predominantly 12 carbon atoms.

of the shampoo.

3 Example V Still another shampoo is prepared as follows:

Percent by weight Sodium salt of the sulfated condensation product of 1 mole of coconut 1 fatty alcohol and 3 moles of ethylene oxide 13.4 Coconut diethanolamide 3.0 Ethyl alcohol 10.0

Propylene glycol 4.0 Methyl cellulose .10 Tetrasodium ethylene diaminetetraacetate .10 Undecylidenediphosphonic acid 2.0 Perfume .50

Water and misc., plus NaOH to adjust to pH 7.4, balance.

The alkyl or acyl group being deriyed from the middle cut of coconut fatty alcohol or fatty acid and containing predominantly 12 carbon atoms.

Hair washed with the above composition in the conventional manner exhibits markedly improved manageability as compared to hair washed with ordinary shampoos. The sudsing characteristics of the shampoo composition above are not materially affected by the phosphono compound incorporated therein. In the above example, the undecylidenediphosphonic acid can be replaced by tridecylidenediphosphonic acid, l-hydroxy-lmethyldecylphosphonic acid, l-hydroxy-l-methyldodecylphosphonic acid, tctradecylaminodi(methylphosphonic acid) or 1-hydroxydodecylphosphonic acid or the alkali metal, ammonium, or lower substituted ammonium salts thereof with comparable results. Similarly, the detergent used above can be replaced by sodium -alkyl benzene sultonate, the alkyl radical of which is an unbranched chain and averages about 12 carbon atoms in length, sodium tetrapropylene benzene sulfonate, sodium 'alkyl glyceryl ether sulfonate, wherein the alkyl radical is derived from the middle cut of coconut alcohol and contains predominantly 12 carbon atoms, or sodium N-acyl sarcosinate, where the acyl radical is derived from coconut fatty acids containing predominantly 12 carbon atoms.

Example VI X and Y, identical switches of human hair (2" by 12") are washed, X with a widely distributed commercial shampoo (an anionic detergent based liquid shampoo composition containing 20.0% by weight triethanolamine alkyl sulfate where the alkyl group is obtained from coconut alcohol and contains predominantly 12 carbon atoms, and also containing minor proportions of perfume, color, clarifying agents, and alcohol to adjust the viscosity, the balance substantially water) and Y with Shampoo B of Example II, Table II, in an identical manner. The switches are allowed to dry in the air after rinsing. When dried, the switches are untangled by combing with the coarse teeth of a hard rubber comb. Each switch is then combed with the fine teeth of the .comb using 10 strokes. At room temperature and a relative humidity of 34% the hair fibers of Switch X spread out and become disarranged due to the repulsion of the electrostatic charges built up on the hair fibers. The appearance of Switch Y washed with Shampoo B exhibits little, if any, indication of static electrification of the hair fibers.

What is claimed is:

1. A shampoo composition which improves hair manageability, consisting essentially of (1) from about 10% to about 30% of a water-soluble detergent salt of a member selected from the group consisting of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 18 carbon atoms and a sulfonic acid or sulfuric acid ester radical, and acyl sarcosinates wherein the acyl group contains from about 10 to about 18 carbon atoms; (2) from about .2% to about of at least one phosphono compound selected from the group consisting of those of the formulae:

(1) RN(CH PO M and (II) Pom:

RC-X

where R is an alkyl radical containing from about 6 to about 18 carbon atoms, X is selected from the group consisting of hydrogen and methyl, and Z is selected from the group consisting of OH, COOM, and PQ M radicals, and M is selected from the group consisting of hydrogen, sodium, potassium, ammonium, and monoethanolammonium, diethanolarnmonium and triethanolammonium; and (3) the balance substantially Water, said composition having a pH Within the range from about 6.0 to about 10.0.

2. The shampoo composition of claim 1 in which component (1) is a sodium, potassium, ammonium, or triethanolammonium alkyl sulfate wherein the alkyl group is derived from the middle cut of coconut fatty alcohol and contains predominantly 12 carbon atoms.

3. The shampoo composition of claim 1 in which component (2) is tetradecylaminodi(methylphosphonic acid).

4. The shampoo composition of claim 1 in which component (2) is l-hydroxy-l-methyldodecylphosphonic acid.

5. The shampoo composition of claim 1 in which component (2) is dodecylidenediphosphonic acid.

6. The shampoo composition of claim 1 in which component (1) is a sodium, potassium, amrnoniurn, or triethanolammonium alkyl glyceryl ether sulfonate where the alkyl group averages about 12 carbon atoms.

7. A process of conditioning and increasing the combability of hair which comprises shampooing the hair in the presence of calcium and magnesium ions in solution with a shampoo composition having a liquid to paste consistency consisting essentially of (1) from about to about of a Water-soluble detergent salt of a member selected from the group consisting of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 8 to about 18 carbons and a sulfonic acid or sulfuric acid ester radical, and acyl sarcosinates wherein the acyl group contains from about 10 to about 18 carbon atoms; (2) from about 0.2% to about 5.0% by weight of a phosphono compound selected from the group consisting of those of the formulae:

( 2 3 2)z and Bil-X where R is an alkyl radical containing from about 6 to about 18 carbon atoms, X is selected from the group consisting of hydrogen, and methyl, and Z is selected from the group consisting of OH, COOM, and PO M radicals, and M is selected from the group consisting of hydrogen, sodium, potassium, ammonium, monoethanolammouium, diethanolammonium, and triethanolammonium; and (3) the balance substantially water; said shampoo having a pH ranging from about 6.0 to about 10.0.

S. The process of claim 7 in which the phosphono compound is tetradecylaminodi(methylphosphonic acid).

9. The process of claim 7 in which the phosphono compound is 1-hydroxy-1-methyldoclecylphosphonic acid.

10. The process of claim '7 in which the phosphono compound is dodecylidenediphosphonic acid.

11. A shampoo composition which improves hair manageability, consisting essentially of (1) from about 15% to about 25 of an anionic detergent selected from the group consisting of sodium or triethanolammonium alkyl sulfate wherein the alkyl group averages about 12 carbon atoms, sodium or triethanolammonium alkylglyceryl ether sulfonate wherein the alkyl group averages about 12 carbon atoms, and sodium or triethanolammonium salts of the sulfated condensation product of 1 mole of coconut fatty alcohol and 3 moles of ethylene oxide; (2) from about .2% to about 5.0% of sodium, potassium, ammonium, monoethanolammonium, diethanolammonium, or triethanolammonium salt of alkylaminodi(methylphosphonic acid) wherein the alkyl radical is nonyl, decyl, undecyl, dodecyl, tridecyl or tetradecyl; and (3) the balance substantially water, said composition having a pH Within the range from about 7.0 to about 8.0.

12. A process of conditioning and increasing the combability of hair which comprises shampooing the hair in the presence of calcium and magnesium ions in solution with a shampoo composition consisting essentially of (1) from about 15% to about 25% of an anionic detergent selected from the group consisting of sodium or triethanolamine alkyl sulfate wherein the alkyl group averages about 12 carbon atoms, sodium or triethanolammonium alkylglycerylether sulfonate wherein the alkyl group averages about 12 carbon atoms, and the sodium or triethanolammonium salts of the sulfated condensation product of 1 mole of coconut fatty alcohol and 3 moles of ethylene oxide; (2) from about .2% to about 5.0% of a sodium, potassium, ammonium, monoet hanolammonium, diethanolammonium, or triethanolammonium salt of alkylaminodi(methylphosphonic acid) wherein the alkyl radical in nonyl, decyl, undecyl, dodecyl, tridecyl, or tetradecyl; and (3) the balance substantially water, said composition having a pH within the range from about 7.0 to about 8.0.

References Cited by the Examiner UNITED STATES PATENTS 2,254,124 8/1941 Stevens et al. 260461.310 X 2,328,358 8/1943 Pikl 260-461310 X 2,607,740 8/1952 Vitale et al. 252-152 2,874,126 2/1959 Epstein et a1. 252152 3,085,067 4/1963 Anderson 252-153 3,086,943 4/1963 Lang 252152 3,125,412 3/1964 Nielsen 25289 3,159,581 12/1964 Diehl 252152 LEON D. ROSDOL, Primary Examiner.

ALBERT T. MEYERS, DONALD E. CZAJA, S. E.

DARDEN, Assistant Examiners. 

1. A SHAMPOO COMPOSITION WHICH IMPROVES HAIR MANAGEABILITY, CONSISTING ESSENTIALLY OF (1) FROM ABOUT 10% TO ABOUT 30% OF A WATER-SOLUBLE DETERGENT SALT OF A MEMBER SELECTED FROM THE GROUP CONSISTING OF ORGANIC SULFURIC REACTION PRODUCTS HAVING IN THEIR MOLECULAR STRUCTURE AN ALKYL GROUP CONTAINING FROM ABOUT 8 TO ABOUT 18 CARBON ATOMS AND A SULFONIC ACID OR SULFURIC ACID ESTER RADICAL, AND ACYL SARCOSINATES WHEREIN THE ACYL GROUP CONTAINS FROM ABOUT 10 TO ABOUT 18 CARBON ATOMS; (2) FROM ABOUT .2% TO ABOUT 5% OF AT LEAST ONE PHOSPHONO COMPOUND SELECTED FROM THE GROUP CONSISTING OF THOSE OF THE FORMULAE: 